FR2915350A1 - PROCESS FOR STABILIZING AND AROMATING UNSATURATED SUBSTANCES AND OILS CONTAINING UNSATURATED AND POLYUNSATURATED FATTY ACIDS - Google Patents

Abstract

Process for the stabilization and aromatization of unsaturated and polyunsaturated oils for aromatic and food use.The invention makes use of the properties of fish oils, in particular for the simultaneous extraction of natural flavoring and antioxidant substances, with a view to to improve their conservation and acceptability.It also allows access to original aromatic compositions in smell, taste and flavor.

Description

METHOD FOR STABILIZING AND AROMATING UNSATURATED SUBSTANCES AND

  OILS CONTAINING UNSATURATED FATTY ACIDS AND POLYUNSATURES STATE OF THE ART

  Animal oils and especially fish oils have been the subject of decades of research and intensive applications because of their interest as food supplements that can bring a benefit for human and animal health, these properties have summarized by I.Mc MURRAY-International Food Ingredients-2007-2-23 / 26

  The consumption of these products is mainly hampered by four obstacles: the need for a daily intake of the order of 1 g / day of an oil containing at least 18% EPA (eicosapentaenoic acid) and 12% DHA (docosahexaenoic acid) (AFSSA report - omega-3 family fatty acids and cardiovascular system, nutritional interest and claims -June 2003-) These unsaturated fatty acids commonly referred to as omega-3 are present mainly in the extracted oils. certain fish (notably sardine, herring, cod, skate, shark), in the form of glycerides and sometimes reinforced by the addition of esters of these same fatty acids. -the unfavorable taste characteristics: taste and smell of rancid and persistent and perceptible fish during their digestion. The chemical instability (oxidability) of the unsaturated compounds present in these oils which produces aldehyde and acidic substances responsible for unpleasant olfactory and taste notes, perceptible in trace amounts, and moreover associated with a toxicological risk. This instability increases by the use of esters of these fatty acids. LIE KEN JIE and AL NATURAL PRODUCTS REPORT-1998- Fatty Acids, fatty acids and their derivatives pp 607-615) -the need to avoid any cooking process that may produce toxic degradation products by pyrolysis and oxidation The oily bodies: glycerides (more or less complete esters of glycerol and saturated and unsaturated fatty acids); the fatty acids resulting from the cleavage of these glycerides by saponification or enzymatic lipolysis; their various esters obtained chemically or biochemically (esterases) are poor solvents, not very powerful in terms of capacity and extraction and solubilization, and moreover unstable.

  Pharmacopoeias have in the past described oily solutes such as camphor oil for which the (vegetable) oil serves as an excipient, a vehicle; which leads to the classification of oily products as pharmaceutical excipients (A.DENOEL - Galenic Pharmacy Course - 1965-Volume II-p263 - University Presses of Liège)

  An example is the so-called "balm tranquil", also called compound henbane oil, pharmaceutical preparation, now obsolete; which uses a vegetable oil to convey an alcoholic extract of medicinal active ingredients; this is indeed an excipient.

  There are currently on the market oily extracts of Garlic, Mistletoe, Hawthorn for therapeutic use, the last two components also from the Pharmaceutical Monopoly (The raw material is listed in the French Pharmacopoeia).

  On the other hand, fish oils belong to the food field; more precisely that of nutritional supplements known as nutraceuticals.

  In the culinary field vegetable oils are used to obtain pimento macerations for pizzas, or even basil for strictly aromatic purposes, but fish oils are not used because of their repellent taste.

  Compared to the usual extraction solvents (which can be used under various conditions: maceration in the environment, reflux extraction, percolation, leaching and which are mainly alcohols, volatile solvents such as acetone, hexane; or else polyols (propylene glycol for example) and which appear on a European official positive list of solvents used for obtaining extracts for human or animal food use); fish oils are not listed and have the following defects: -High cost - A reduced solvent power and difficult to manage. - The impossibility of concentrating the extracts obtained and to recycle all or part of the oil used as a solvent. An instability directly related to the presence of unsaturated compounds

  Fish oils, and more generally unsaturated oils, have not been used heretofore as extraction solvents by any industry; especially in the Food and Pharmaceutical industry for the reasons already mentioned and in particular. -Repusting taste and odor -Instability, accompanied by the risk of producing toxic substances

  The flavoring materials and also the antioxidants are never extracted using fish oils and more generally unsaturated oils.

  By fish oils is meant any oily extraction product extracted from marine organisms composed mainly of glycerides of saturated fatty acids, unsaturated and polyunsaturated and any composition comprising a marine oil associated with saturated fatty acid esters, unsaturated polyunsaturated.

  There is indeed a whole range of marine oils: -The most classic, especially from sardine, herring, herring, cod, ideally include: 18% eicosapentaenoic acid (EPA) 12% acid docosahexaenoic (DHA) (% expressed, by convention, in relation to the total fatty acids present in the oil). - Reconstituted oils resulting from the assembly of various oils of various fish -.Oils reinforced by the addition of esters of fatty acids from the extraction, saponification, extraction then semisynthesis by chemical or enzymatic; this route makes it possible to obtain extremely high levels of unsaturated fatty acid esters of interest (in particular EPA and DHA).

  Faced with the difficulties mentioned above, the producers and formulators have hitherto resorted to the following palliatives: - the use of antioxidants - the protection against oxygen - the addition of flavoring and / or masking substances (US Patent 6,576,253 claims the combination of malto-dextrins and natural flavors))

  These palliatives are insufficient and do not allow long-term preservation and satisfactory taste acceptability, with an acceptable additional cost. All of these unresolved issues so far have been exposed in AROMES INGREDIENTS ADDITIVES- 2007-68-45 / 51

  It should be noted that: 1-The use of antioxidants is limited qualitatively and quantitatively by European and national regulations concerning the use of food additives. 2-These antioxidants have an extremely limited antioxidant capacity and can not alone stabilize a raw material and a fortiori a formulation. 3-Empirically, formulators have observed synergies with associations of antioxidants, without an understanding and a theory of this effect is possible; even more antioxidants or their own oxidation products can be frequently pro-oxidants and accelerate the degradation process. 4-Protection against oxygen is relatively effective: by inerting, nitrogen for example; or partial vacuum, for industrial storage; or by encapsulation (soft capsules or microcapsules), which is achievable with high costs and inevitable dilution of the oil which interferes with the ease of ingestion. The encapsulation makes it possible to obtain storage times of three years, by the barrier effect against the oxygen used and by the coating of the product whatever its state.

  This is the reason why encapsulated products are not easily digested because of the possible hints of fish.

  5-The addition of flavoring or masking substances generally constitutes a plating, or a juxtaposition of taste and olfactory notes, which is added in a more or less happy way to oxidized notes and fish, and proves incapable of inhibiting their training. Generally the duration of perception of taste sensations of the aromatization is lower than that of the notes fish and oxidized which are extremely persistent 6-Considered individually or in synergy these processes and strategies bring considerable additional costs, without noticeable benefit. The general strategy is systematically based on the use of additives: flavors, masking agents, anti-oxidants, encapsulation agents; without exploiting the functionalities of the marine oils to be stabilized (their possible extractive capacity), nor knowledge of the compatibility of said additives with the natural components of these oils. The control of the taste acceptability of these assemblages remains problematic and constitutes a major obstacle for the user to observe the consumption of the recommended doses. (US Patent 4,853,247) DESCRIPTION OF THE INVENTION

  * Unexpectedly we observed that the fish oils possessed a sufficient and specific solvent power towards anti-oxidants naturally present in certain spices, and certain condiments and aromatics used in Culinary Art or in the Aromatic Industry in addition to their power. solvent of flavoring substances.

  These properties allow the simultaneous extraction, simultaneously, antioxidants and aromatic substances and flavors of various plants and plant parts commonly used as condiments, spices or herbs.

  In general, plants and their fractions (seeds, leaves, roots, fruits) have been widely studied for their olfactory and taste properties, based on the results of the most efficient methods of analysis (chromatography in phase gas (GC), CPG coupled to mass spectrometry or GC-olfactometry); this allowed us to identify only the volatile components of the essential oils they contain. On the other hand, their composition in natural antioxidants: unsaturated compounds and polyphenols remains poorly known.

  Those skilled in the art also know, empirically: 1-That natural antioxidants complex mixture, are generally more effective than chemical substances obtained from their purified extracts (Rosemary, oregano and their respective extracts are typical examples) 2-That the protective effect of any antioxidants is limited and requires conservation in the absence of air. (Hamilton et al., J. Am Oil Chem. Soc. 1998-75-7-813 / 822) (M.OZCAN-Journal of Medicinal Food-2003-6-3-267 / 270) As a result, it took us carry out a comparative study of the effectiveness of various spices, t aromatics and condiments.

  The validation of the effect of this or that antioxidant is generally obtained from the measurement of global chemical tracers (peroxides index, thiobarbituric acid test, iodine number, fatty acid determination, search for compounds oxidation tracers, (for example limonene oxide in the case of limonene), another approach is to voluntarily oxidize the presumed stabilized preparation and to compare its relative stability, in fact its degradation profile, to an untreated control: Rancimat test for example.

  All these tests are either fragmentary (measurement of tracers more or less arbitrary) or excessively aggressive (when it comes to disassemble a global protective power against the) xydation), and, therefore, hardly predictive of the conservation of the sample in question.

  In the case of fish oils, trace amounts of oxidation compounds are sensory detectable with a sensitivity much higher than that of all conventional methods; this results in an extreme severity of the test because of the exploitation of the sensory results in all or nothing: the appearance of an off-note or note-parasite, fish or rancid leads us to reject the formulation considered. (VENKATESHWARLU and Al-J.Agric.Food.Chem-2004-52 (2) -311/317) These oxidation products are often accompanied by traces of aliphatic amines (triethylamine, in particular) resulting from the partial degradation of the fish or organs (livers) of the fish used. These olfactory and taste tests make it possible very quickly (within a maximum of three weeks) to observe the beginning of a deterioration: this is a considerable advantage over chemical methods. (HAMILTON R.J. and AlJA.Am Oil.Chem Soc-1998-75-N 7-pp813 / 822) The application of the extractive process which is the subject of the present invention to various extracts made it possible to observe the effects following: 1-There is a great variability in the antioxidant stabilizing potential of the various oily extracts of the plants studied. 2-For the same plant species the effects obtained can vary significantly from one batch to another, particularly depending on the duration and storage conditions of the plant material used. These two characteristics are known to those skilled in the art. 3-Compared with the most commonly used or recognized as the most effective anti-oxidants: BHA (butylhydroxyanisole) BHT (butylhydroxytoluene) Ascorbyl palmitate Natural tocopherols (extract) Association of ascorbyl palmitate and tocopherols, it is found, in the context of the present invention, for certain vegetable extracts by fish oils, oxidation protection performance significantly higher and qualifiable by: -the improvement of the shelf life 25 -the improved stability in conservation in opened flasks, that is to say having a head space, therefore a significant volume of oxygen. This constitutes a model for studying oxidative degradation, representative of conditions of use of the oil without particular precautions.

  To date, these facts have not been reported and can not be reported to the state of current knowledge on the composition of the plants used nor to any comparable extractive preparation. 4-If reference is made to the natural plant antioxidants recognized and listed below, it is found that their liposolubility is often theoretically favorable to extraction by an oil.

  Under these conditions, a relative uniformity of protection performance against oxidation should be observed between the various plant extracts studied, this is absolutely not the case and this observation is opposed to any generalization.

  This means that, unexpectedly; in some plants or parts of plants (leaves, seeds, fruits, roots, bark): -or many powerful antioxidant compounds, and not described so far, naturally present, are extractable by fish oils. or the anti-oxidant compounds or part of these compounds exist in the plant in a physical state or in particular chemical combinations and not described to date, which allow their extraction by fish oils under the conditions of the present invention.

  Table of main natural antioxidants (**)

  Solubility in oils ... in organic solvents (***) Vitamin C Nil Null Vitamin E Good Good Folate Nil Nil Carotenes Moderate Good Polyphenols (*) Good Good Polyphenols salified Nil Nil Flavonoids Medium Medium Lycopene Good Low Coenzyme Q10 Good Good Documentary origins: (*) - P.Brat- CIRAD-Montpellier (**) - ANTIOXIDANTS IN FOODK.Pelli-M.Lyly Flair Flow Europe 4- INRA 25 30 35 - 9 - (**) - V. NEDYALKA and AL-European J.of lipid science and Technology-2001-103-11-752 / 767) (* * *) Merck Index

  Rosemary extracts are the reference in terms of natural phenolic antioxidants. Given the weakly acidic properties of phenols, various strategies exist for the extraction: 1-solvent extraction: methanol, acetone, generally hot, followed by evaporation and the dissolution of the extract in a vegetable oil ( E.STEFANOVITS and AL-Acta Biologica SZEGEDIENSIS-2003-47 (1-4) 111/113) (D.BANDONIENE and AL-NAHRUNG-2001-April-45 (2) -105 / 10) 2-Making the most of the solubility in water of the salts obtained by the action of a base on phenols (US Pat. No. 4,012,531), or that of acidified extracts in organic solvents (US Patent 4,354,035) 3-The use of solvents fluorinated. (US Patent 6,855,349) 4-The use of gases in the supercritical state, which under these conditions behave substantially as organic solvents.

  In no case is it possible to use a vegetable or animal oil as extractant.

  5-The choice of spices and herbs studied took into account the acceptability of the flavor and the smell of the extracts obtained. Surprisingly some of these oily extracts are not only able to extract complex natural antioxidant substances, but also taste and olfactory flavoring materials, not only acceptable but also extremely rich, aromatic and fine complex and complex. qualitatively distinct from the usual aromatic extracts (essential oils, oleoresins, various extracts).

  This is explicable by the absence of use of volatile solvents, the absence of the use of concentration; the absence of any use of heat at any stage of the process, which minimizes the risk of degradation, but also the fact that many flavoring substances exist in the plant in a physical state or in chemical combinations (heterosides for example) which escape the usual techniques of extraction. (Research theme of CIRAD-Montpellier)

  This means that the hypothetical substitution of extracts obtained with the aid of fish oils, a mixture of essential oils and or oleoresins, or even extracts obtained by other means, would neither make it possible to restore completely the flavor and smell, nor the antioxidant power of extracts obtained with fish oils.

  It is important to emphasize that a conventional aromatisation-stabilization such as that mentioned in the preceding paragraph is in no way interchangeable or substantially equivalent, in comparison with the corresponding plant extract obtained under the conditions of the invention. with fish oils. The process which is the subject of this document could be compared with the conventional technique of enfleurage of extracts for perfumes; with the difference that the extractive materials used by the latter process are significantly different, separated in-fine extracted materials and that the present process is not the perfumery 20 and raw materials for this use. In addition, the extraction agents used in enfleurage are obligatorily neutral on the sensory plane.

  6-The oily animal extracts, aromatic obtained, also have excellent preservation qualities; unexpectedly, stabilized unsaturated oils, compatible and stable aromatic extracts (not yet described), and taste-tolerant formulations having an undoubted food status are thus obtained. This radically differentiates the extracts obtained from conventional assemblies obtained by the addition of flavors and stabilizers.

  7-With the above reservations, it goes without saying that the transposition of the process to other unsaturated compounds, such as the terpene compounds which are part of the composition of many raw materials and aromatic extracts is practicable. 10 -11-

  We thus arrive at a novel concept of building-block or premixture that can be of great use, under the condition of gustatory and olfactory compatibility in the final product between the extractive material (a terpene for example) and the flavoring and stabilizing agent. extracted from a plant by this terpene.

  By way of example, an extract using a vegetable oil can be designed as an extraction solvent for sage, rosemary or clove, etc .; associated with an essential oil of sage or rosemary, or clove ... having improved preservation without having to resort to the addition of a conventional antioxidant.

  8-Unexpectedly, we observe for certain extracts the obtaining of unpublished aromatic notes which result either from the juxtaposition of the aromatic notes specific to the fish oil implemented with those of the condiment, the flavoring or the spice. used; or the extraction of original flavoring materials. There is here a source of potential aromatic innovations which also has the advantage of simultaneously containing antioxidant substances useful not only for the stabilization of the oil used, but also the stabilization of the flavoring substances extracted. 9-Although the oils are considered as poor solvents, and the vegetable substrate to be extracted is whole or contused (seed-leaves) one finds unexpectedly, that the extraction of the aromatics and antioxidants substances is carried out in relatively short lead times comparable to the usual maceration times in solvents such as alcohol, glycerol, propylene glycol or even liquid polyoxyethylene glycols; the latter being used for the cosmetic and pharmaceutical industry.

  Those skilled in the art know that the extraction is limited by the diffusion rate of the chemical species of interest (aromas and antioxidants); it is therefore unnecessary to carry out prolonged and intense agitation of the mixture during maceration. Therefore the diffusion of the chemical species of interest should be extremely slow, unexpectedly, the extractive equilibrium is reached in a few weeks, which suggests that the substances of interest are in a physical form or an unknown chemical structure but conducive to and favorable to the process described in the present application. -12-

  10-The extraction is also carried out at room temperature (20 C +/- 5 C) which is the guarantor of protection of the substances of interest: aromas and antioxidants. and differentiates the claimed process from the usual extraction techniques of the antioxidant compounds in particular.

  11-Finally, the physical state of the plants (seeds, dried leaves) contamined or not does not influence significantly the speed of the extractive process.

  These last two observations were a priori unpredictable given the state of knowledge on the properties of fish oils.

  12-Compared with antioxidant extracts of natural origin, the equivalent dose of the plant is of the same order of magnitude.

  Indeed, if we consider that a maximum content of 10% weight / weight in plant relative to the oil is sufficient to achieve the dual objective of aromatization and stabilization, it is virtually the same for plant extracts usual antioxidants obtained by drastic techniques (solvents, high extraction temperatures and concentration); thus the anti-oxidant extract of Rosemary which refers to: 1.0 Kg of rosemary provides about 0.13 Kg of crude antioxidant extract, the recommended use dose is at least 200mg / Kg or 500mg / Kg of finished product, ie 5% plant equivalent.

  To the extent that the claimed process necessarily leads to a state of equilibrium, compared to a conventional extraction process aimed at the exhaustion of the substrate to be extracted, it can be considered that economically and technically the processes are comparable; the situation is quite different in terms of quality: because of the non-aggressive conditions of the claimed process and the nature of the active chemical species (antioxidants) extracted, extraction with fish oils constitutes a receivable alternative. - 13 -

  The application examples used On the one hand fish oils rich in omega-3 unsaturated fatty acids and alkyl-glycerols Shark or Ray fatty liver oil Free fatty acids: less than 0.5% iodine: minimum 80g / p 100g Minimum saponification level 120mg KOH / lg Unsaponifiable: minimum 20% Minimum omega-3 content: 40% Oleic acid content: 20%

  On the other hand Fish oils (Sardine, Cod, Herring, Salmon, rich in Omega-3) Minimum content: EPA: 10% DHA: 20% GENERAL DESCRIPTION OF THE PROCESS:

  The fish oil resulting from the extraction and purification process is supplemented with the plant material to be extracted beforehand if necessary. Experience shows that a maximum content of 10% by weight per weight of the plant relative to the oil, is usually sufficient. Indeed higher concentrations pose problems of dispersion of the plant to be extracted and may lead in some cases to a saturation of the extractant (the oil used) in substances of interest (aromas, antioxidants). Vegetable mixture and fish oil is kept away from air and light, under inert gas (nitrogen) or under partial vacuum; at room temperature (20 C +/- 5 C) for at least 20 days. A longer term does not present any risk or significant benefit. Every five days, by appropriate means, and without introducing air, the maceration is resuspended to facilitate the action of the extractant. It is found that the decantation of the plant material is relatively fast and that all the extracts are easily clarified, even in the case of pulverulent raw materials. At the end of extraction, after decantation of the supernatant, protected from the air; the solid residue can be pressed and its product, clarified, added to the supernatant. The supernatant is clarified, protected from the air; and packaged in inert, watertight, opaque and completely filled or nitrogen-inerted packages, if filling can not be complete. This process also makes it easy to standardize the overall protective and flavoring power by assembling extracts of different potency for both antioxidants and aromatic materials.

  Preferably, the extract, after control, can be directly divided into unit doses: opaque soft sachets, sealed, sealed or single-dose vials. The final control makes it possible to ascertain the physico-chemical and microbiological characteristics of the extract obtained; it is accompanied by the determination of chemical oxidation tracers and taste comparison with reference sample extracts, the latter test is decisive. This process has the advantage of being able to integrate easily with the normal production sequence of a fish oil; it requires, in addition to controlling the quality of the oils used, that of the plant materials used and in particular: the shelf life between harvest and use, traceability the residual moisture content of the plants or parts of plants used microbiological quality (search for spores of anaerobic microorganisms in particular) taste quality These controls are familiar to those skilled in the art who use condiments, spices or aromatics.

  The oily medium being a priori favorable to the development of anaerobic microorganisms, we also practiced tests on fresh plants, not dried (Thyme, Savory, Sage, Shallot, Onion) .15 -15- In these extreme and favorable conditions the development of such contaminations; no revivification of spores was observed and in general no development of bacteria, yeasts or molds was found, but all the extracts made was less protective of oxidation and especially less powerful extracts obtained from dry plants or their dried fractions, (dry weight equivalent).

  The use of dried raw materials minimizes the risk of contaminations, reduces the risk of uncontrollable enzymatic reactions (oxidases, peroxidases, esterases) and remains compatible with industrial management of the extractive process.

EXAMPLES

  Two types of fish oils have been systematically used comparatively: An oil rich in omega-3 polyunsaturated fatty acids, in particular EPA and DHA: called oil A An oil rich in polyunsaturated fatty acids of the Omega 3 type, in particular EPA and DHA and rich in alkyl glycerols: called oil B For each type of oil, two controls have been preserved: - One free of antioxidant (s) corresponding to the original raw material used: Control oil 1 -The second supplemented with BHT, considered as the reference antioxidant and in the limited scope of modeling. Control oil 2 Indeed, BHA and BHT are chemically defined antioxidants that are potent but suspect in their use in food.

  The comparative sensory analysis was carried out after 3 weeks, then 6 months of storage at room temperature (for the only tests deemed satisfactory after 3 weeks of storage), in the dark, in a sealed glass bottle having a headspace of 50%. This large, air-rich head space is a conservation study model, with no special precautions. After three weeks of storage, the two oil oils 1 and 2; presented rancid taste and olfactory notes.

  EXAMPLE 1 THYM EXTRACTS (Thymus vulgaris) 1-1-Thym dried, in leaves, origin Morocco, initial storage of 24 months before use After 3 weeks: Extracts A and B, greenish, limpid, have an odor of linen. Tastefully a note fish attack (at the beginning remains perceptible then disappears in favor of the thyme note which persists durably, without a taste of fish.) In these conditions this test was not continued, although the obtaining of an anchovy-thyme note can be conceived and be judged acceptable in presentation on appetizer croutons 1-2-dried thyme, leaves, origin France, initial storage 12 months before use After 3 weeks: The oily extract B is green, clear, it has a weak smell of thyme, the smell of rancid and fish is undetectable.The thyme flavor is intense, without flavor, nor aftertaste of fish oil, it is reminiscent of aromatic notes pizza L ' oily extract A is noticeably less potent, but presents no taste defect After 6 months: extracts A and B have retained their satisfactory initial characteristics, compared to the corresponding controls at +4 C.

  The application to grated carrots, at a dose of 1g of oil for about 50g of vegetables; which corresponds to the recommended daily intake, communicates to them a frank thyme note and exhausts the overall bitterness, the latter is corrected by the use of olive oil.

  These extracts combine easily with lettuce salad or celery rémoulade. The application on croutons of toast remains the most acceptable.

  1-3 Fresh thyme, undried, harvested at the end of flowering. After three weeks the oily extracts A and B have a faint odor reminiscent of flaxseed oil and a poor fishy taste. - 17 - Globally the aroma more evokes that of Basil than that of Thyme After six months of conservation, the characteristics have not changed, no noticeable degradation.

  Example 2 EXTRACTS FROM A MIX OF SPICES Powdered said FOUR SPICES defined as a mixture of: Cinnamon, Clove, Ginger and Nutmeg Origin India- Shelf life before use unknown. After three weeks the oily extracts A and B have a smell of fish and cinnamon taste, unexpected is not unpleasant. The preservation test was not continued for lack of sufficient antioxidant activity.

  EXAMPLE 3- EXTRACT OF GIROFLE (Eugenia caryophyllata) called whole cloves, shelf life before use unknown. After three weeks the oily extracts A and B present a clean fish note, associated with a note eugenoloxidized, unpleasant. This illustrates that a strong antioxidant such as eugenol is unsuitable for the protection of marine oils; which is in line with example 2.

  EXAMPLE 4-EXTRACTS OF INDIA WOOD, whole seeds (Pimenta racemosa) After three weeks the oily extracts A and B show a pleasant odor free from pest notes and a slightly resinous taste with the exception of any other note of taste. After six months the characteristics are unchanged, without appearance of oxidized notes or fish.

  EXAMPLE 5-EXTRACTS OF CURRY POWDER The curries correspond to mixtures varied according to the user countries Composition: Turmeric, Coriander, Mustard, Fennel, Cumin, Shallot, Pepper, Celery, Fenugreek.

  After three weeks, the oily extracts A and B have a very pleasant smell of curry and an identical taste, without parasite notes. After six months of storage, the characteristics of the extracts have not changed. -18-

  EXAMPLE 6 CUMIN EXTRACTS Seeds- (Cuminum cyminum) and CARVI (Cartan carvi) Two samples of different origins were tested.

  The results were found strictly comparable. After three weeks -The oily extract A is clear, yellowish-green in color with a clear odor of caraway, with no detectable traces of fish odor or oxidation products. The taste of cumin is powerful, persistent, without oxidized notes or fish and without after-taste. O The oily extract B has similar characteristics with slightly less power, the product is milder, rounder in aromatic terms. After 6 months: Extracts A and B have retained their satisfactory initial performance.

  The application of these extracts Mash salad and Celery rémoulade gives very pleasant and very acceptable seasonings. The tomato salad has the taste of cumin.

  The extracts of Carvi behave in a quite comparable way.

  Carvi is botanically close to Cumin, this does not make it possible to extrapolate the positive effects obtained with umbelliferous seeds for example because there is not necessarily a concordance between the botanical classification and the chemical composition of the various plants of a plant. same botanical family, this reality is known to those skilled in the art.

  EXAMPLE 7-EXTRACTS OF ORIGAN dry leaves (Origanum vulgare) Origin France, shelf life before use unknown. After three weeks: The oily extract A is clear, yellowish, almost odorless: the notes of oregano, oxidized and fish are imperceptible.

  Gustative: we perceive warm notes overall Mediterranean cuisine free from parasitic notes, including fish and oxidized. The oily extract B: is very comparable, but substantially less powerful. Controls 1 and 2 are oxidized. After 6 months: extracts A and B have retained their satisfactory characteristics. -19- In application in tomato salad fish notes reappear, there is incompatibility, and this is the only case listed here between this food and the oily extracts considered. Acceptability on croutons of toast is satisfactory: lack of notes and aftertaste of fish.

  Oregano and thyme are botanically close, but their chemical components are not necessarily similar or functionally equivalent, for this reason the production of vegetable extracts by unsaturated oils can constitute a test of evaluation of the antioxidant potential of a plant or a plant extract.

  EXAMPLE 8 MUSCADE EXTRACTS, coarsely grated fruit (Myristica fragrans) Origin India - Shelf life unknown. After three weeks: The oily extract B is limpid, not very colored, and has a clean smell similar to that of linseed oil. The taste is distinct from that of nutmeg; floral, it recalls the crudités (radish) Without parasitic flaw of oxidation or note fish. In application on a crouton of toast the whole is extremely pleasant: notes of type cracker for aperitif. The oily extract A is very clearly less powerful, but without taste defects After 6 months: the performances of the extracts A and B are at least preserved, even improved: aromatic notes more balanced, very aperitive.

  When applied in a tomato salad, the taste is unusual, not unpleasant. Associated with a smoked fish (herring) the extract softens the smoke notes and as the cumin extract brings frank salmon notes free of oxidation.

  These extracts, apart from their stabilizing effect, offer the flavourist and the cook the potential to create or reinforce new flavors.

  Associated with the tomato salad, the oily extract B communicates cooked notes, unexpected confit; this observation reinforces the preceding remark. - 20 -

  EXAMPLE 9-CARDAMOM dry fruit (Elettaria cardamomum) Origin and shelf life unknown Two different samples were used one (formerly practically discolored) the other, newer, pistachio green After three weeks 9-1- oily extract A from recent cardamom (green) is limpid, yellow with strong cardamom odor, no fish and oxidized parasitic notes. The taste is only that of cardamom, powerful and durable, without a taste of fish. The oily extract B is qualitatively comparable, but its potency would make it possible to use an initial extractive mixture with 7 or 8% cardamom.

  In application in the seasoning of grated carrots, in the presence of lemon juice or vinegar the acceptability is very satisfactory, without rancid notes. The same goes for seasoning a tomato salad. The app on croutons of toast is the most palatable; it's the same with a pizza. The addition to smoked fish preparations gives unexpected results: the flesh of smoked herring is perceived as that of a salmon very delicately prepared. In these various applications: no rancid or oxidized after-taste is perceptible and only the taste of cardamom persists.

  9-2- The oily extract A from old cardamom (discolored) has a fugitive fish attack note, relayed by disappointing clove notes After 6 months, oily extract samples A and B, described in 9- 1 and 9-2 have retained satisfactory sensory characteristics.

  EXAMPLE 10- SAGE EXTRACTS, leaves (Salvia officinalis) 10-1-Dry leaves: Origin Germany-Shelf life 18 months. (A witness unseasoned fresh sage leaf, was also used in comparison) After three weeks: Oily extract A is clear, with a single scent of sage. Gustatively we observe a sage note associated with a trace of fish note. The potency of the sage note is such that the implementation of the plant could be decreased and reduced to 6 or 7% (w / w) in the initial extractive mixture. In application, the addition of seasoning extracts of grated carrots, tomatoes is very satisfactory and the parasite fish note becomes unapparent, even in the presence of lemon juice or vinegar. The preservation test was not continued because of the average performance as an antioxidant and because of the presence of thujone which presents a risk in case of repetitive use, which is the rule with the diets. enriched in polyunsaturated fatty acids.

  This type of extract can be considered simply as a representative model of the antioxidant functionality of oily extracts of sage.

  10-2-Fresh leaves: After three weeks, extracts A and B, limpid, green; do not have a fishy smell. Tastefully the fish note is found, associated with an unpleasant soapy taste.

  EXAMPLE 11 EXTRACTS OF Dried, Crushed ECHALOTE BULBS (Allium ascalonium) After three weeks, extracts A and B are clear, golden yellow and have a pleasant sulfur odor associated with a sardine note Acceptability is good, the degradation is not aggravated compared to the witnesses of the starting oils, but its typicity and the nature of the parasitic note motivated the stopping of the test.

  EXAMPLE 12 - EXTRACTS OF PILI-PILI or Whole Fruit Bird Pepper (Capsicum frutescens) After three weeks the extracts A and B are bright yellow and have a simple juxtaposition of the piquant character to fish notes which have not been aggravated by to the original witness and cast doubt on the interest and acceptability.

  We are here typically in the case of a classic aromatization that juxtaposes aromatic or tasty notes with undesirable aromatic and taste notes, without complementarity or synergy.35 - 22 -EXAMPLE 13-CORIANDER EXTRACT seed (Coriandrum sativum) After three weeks oily extracts A and B have an odor and a taste of fish.

  EXAMPLE 14-MACIS POWDER EXTRACTS, dried arils of Myristica fragrans. After three weeks, the oily extracts A and B are clear and have a golden yellow coloring with a pleasant floral scent, very rich and very fine. Tastefully there are no noticeable fish and oxidized notes, the overall sensation is slightly peppery with a very sweet, green floral bouquet. After 6 months, the characteristics are unchanged. If these aromatic characteristics are known for Macis in non-oily extracts, its stabilizing power remains unpublished.

  EXAMPLE 15 - PEPPER EXTRACTS: Black pepper and crushed green pepper (Piper nigrum) After three weeks, the strongly colored extracts A and B have fish notes.

  EXAMPLE 16-EXTRACTS OF SPRAYED CINNAMON (Cinnamomum zeylanicum) After three weeks the extracts A and B are clear, slightly greenish, with a floral odor and a taste unoxidized and cinnamon linseed oil, unexpected, pleasant. The originality of the tasting notes obtained would require the study of the culinary applicability in aperitif crackers for example. After six months, the characteristics have not changed: very good conservation.

  These extracts can be considered as models of stabilizing activity and obtaining original flavors for the Aromatician and the Cook.

  EXAMPLE 17-EXTRACTS OF ANETH, + Dry leaves (Anethum graveolens) After three weeks the extracts A and B are clear, of greenish color, the smell of dill is modified and the taste of fish is present, although honed .

  EXAMPLE 18-BASIL EXTRACTS Fresh leaves (Ocimum basilicum) After three weeks, extracts A and B are clear and have a parsley odor combined with that of the fish note, as well as a rancid taste.

  Although acceptability remains good, the trial was not continued. -23 -

  EXAMPLE 19-EXTRACTS OF SARRIETTE, fresh leaves (Satureia hortensis) After three weeks, extracts A and B are clear and have a pleasant fruity odor.

  The taste remains that of a fresh fish, moderately intense. There is no oxidized aftertaste or fish. Dry savory very quickly loses its aromatic qualities and has therefore not been tested. The use of oily extracts of savory seems to be reserved for a short-term use, although the synergy with the fish notes is aromatically promising.

  EXAMPLE 20 EXTRACTS OF COCOA Powder (Theobroma cacao) These extracts were made at the concentration of 5% (w / w) because of the aromatic power of the cocoa.

  After three weeks, extracts A and B present fish notes of the tuna and sardine type, without parasitic notes or cocoa notes. The only potential interest of the trial is the potentiation of fish notes by cocoa extracts; the stabilizing effect, real, remaining marginal because one of the objectives remains the masking of fish tastes.

  EXAMPLE 21 Extracts of Persil, Fresh Leaves (Petroselinum sativum-Petroselinum crispum var neapolitanum) After three weeks the extracts A and B are clear, colored green and have fishy notes. EXAMPLE 22: CHICOLATE EXTRACT, fresh leaves (Allium schoenoprasum) After three weeks the extracts A and B have an alliaceous odor, and a taste of mussel broth which has only an aromatic interest.

  EXAMPLE 23: ROSEMARY EXTRACT fresh leaves (Rosmarinus officinalis) Rosemary extracts, as indicated above, are referred to as antioxidants. The dry leaves of Rosemary degrade very quickly, especially by oxidation and are quickly invaded by molds that accelerate their degradation.25 - 24 - After three weeks the extracts A and B are limpid, green; without notable oxidation, with a discreet fish note but with an unpleasant soapy and earthy flavor.

  It appears in these conditions that the extraction of antioxidants Rosemary marine oils is insufficient and that some of the flavoring materials of this plant are inconsistently incompatible and insufficient to cover the fish notes.

Claims (4)

  1- Process for obtaining stabilized extracts against oxidative degradation and having satisfactory taste acceptance; using marine oils containing unsaturated fatty acids, their compositions as well as the marine oils reinforced, in particular fish oils, by the maceration under controlled conditions of said oils with plants or fractions of plants (fruits, seeds, leaves, roots, bark) in the fresh or dry state, preferably dry.   2- A method according to claim 1, wherein an oil containing unsaturated compounds allows, by direct contact in easy and non-aggressive conditions vis-à-vis the substances of interest that are the antioxidants and natural flavors of plants to simultaneously obtain an aromatization of the extract and protection against the risks of oxidative degradation.   3- A method according to the preceding claims, wherein the plant is selected from Thyme, Wood of India, Cumin, Caraway, Oregano, Nutmeg, Macis, Cardamom, Cinnamon.   4- Use of the oily extracts obtained according to the preceding claims, either in the state, or in compositions for human or animal food use, or for food supplements or for the aromatic, pharmaceutical or cosmetic industries. 25